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EP0758221B1 - Hair-treatment agents - Google Patents

Hair-treatment agents Download PDF

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Publication number
EP0758221B1
EP0758221B1 EP95917328A EP95917328A EP0758221B1 EP 0758221 B1 EP0758221 B1 EP 0758221B1 EP 95917328 A EP95917328 A EP 95917328A EP 95917328 A EP95917328 A EP 95917328A EP 0758221 B1 EP0758221 B1 EP 0758221B1
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EP
European Patent Office
Prior art keywords
polymer
water
esters
hair
polymers
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
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EP95917328A
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German (de)
French (fr)
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EP0758221A1 (en
Inventor
Winfried Emmerling
Hans-Peter Hofmann
Rainer Kade
Ludwig Schieferstein
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Publication of EP0758221A1 publication Critical patent/EP0758221A1/en
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Classifications

    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00Preparations for care of the hair
    • A61Q5/06Preparations for styling the hair, e.g. by temporary shaping or colouring
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/8141Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • A61K8/8152Homopolymers or copolymers of esters, e.g. (meth)acrylic acid esters; Compositions of derivatives of such polymers

Definitions

  • the invention relates to the use of an insoluble polymer with a Glass transition temperature between -20 and + 70 ° C, consisting essentially of Monomers selected from the group consisting of esters of acrylic acid and esters of Methacrylic acid and styrene include in hair treatment products, for the treatment of Hair with the proviso that the hair treatment composition containing conventional cosmetic Components present in the form of an aqueous dispersion of this polymer continue contain a water-soluble polymer and contain water as the only solvent.
  • Hair treatment agent in the form of aqueous solutions or emulsions of polymers with Acrylate monomers are, for example, from international patent applications WO 94/02112 and WO / 01079 as well as European patent application 0 590 604.
  • Aqueous hair treatment products, the water-insoluble polymers and for these Suitable water-insoluble solvents are from the international Patent application WO 92/21319 known.
  • the international patent applications WO 91/15187 and WO 91/15186 disclose aqueous hair treatment agents, the polymers with certain solubility parameters as well as non-aqueous solvents Solubilization of these polymers included.
  • German Offenlegungsschrift 42 24 761 water-soluble or water-dispersible polycondensates with glass transition temperatures above +20 ° C in hair treatment products.
  • the hair treatment agents used according to the invention are in the form of aqueous dispersions before and contain an insoluble polymer.
  • aqueous dispersions include such dispersions understand, whose outer phase consists predominantly of water, water being the only one Is solvent.
  • a polymer is insoluble in the sense of the invention if it is in at room temperature Water is less than 1 wt .-% soluble.
  • the water-insoluble polymers used according to the invention have glass transition temperatures between -20 ° C and +70 ° C. Polymers with glass transition temperatures between -10 ° C and +50 ° C, especially between +10 ° C and +30 ° C are preferred.
  • the water-insoluble polymers used according to the invention consist of essential, d. H. to at least 80 wt .-%, based on the polymer, from esters of Acrylic acid and / or methacrylic acid and / or styrene.
  • esters of these acids come as esters of acrylic or methacrylic acid linear and branched, saturated and unsaturated aliphatic alcohols, aromatic alcohols and aliphatic-aromatic alcohols.
  • Prefers are esters with linear and branched, saturated and unsaturated aliphatic Alcohols with 1 to 22 carbon atoms.
  • Such alcohols are, for example Methanol, ethanol, n- and iso-propanol, n- and iso-butanol-1, n-pentanol-1, n-hexanol-1, n-heptanol-1, n-octanol-1, n-octanol-2, n-decanol-1, n-dodecanol-1 (lauryl alcohol), Myristyl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, oleyl alcohol and Linoleyl. Alcohols with 1 to 6, in particular with 1 to, are particularly preferred 4, carbon atoms.
  • esters acrylic and methacrylic acid with the corresponding alkoxylated, in particular ethoxylated alcohols are also usable according to the invention.
  • Degrees of alkoxylation of from 1 to about 10 can be present.
  • Styrenes as defined in the application are also compounds that have a short chain Have alkyl group, especially a methyl group, on the ⁇ -C atom of the vinyl group.
  • the content of styrene groups in the polymer is preferably less than 70% by weight, based on the polymer, limited, since it may otherwise be difficult, polymers with glass temperatures in the range mentioned.
  • polymers can be used according to the invention which consist of only a few monomers. So agents with homopolymers or Copolymers of only two monomers have surprisingly good properties. It can therefore be preferred in the context of the teaching according to the invention such homo- To use copolymers.
  • the water-insoluble polymers therefore also preferably contain in addition to Acrylic acid esters, methacrylic acid esters and styrenes are no further components, where Impurities in the monomers and compounds which cause the chain termination, should not be considered as additional building blocks.
  • the average molecular weights of the polymers used according to the invention are in the Usually between 20,000 and 2,000,000; Values between 50,000 and 500,000 have been proven to be particularly advantageous. Those skilled in the art are able to: To obtain polymer synthesis molecular weights in a desired range, known.
  • the hair treatment compositions used according to the invention contain the insoluble polymer, depending on the type of hair treatment product that has no restrictions is subject to, preferably in amounts of 0.1 to 30% by weight, in particular 1 to 20% by weight, based on the total mean.
  • the agents according to the invention are distinguished in comparison to agents with dissolved Polymers from very low viscosities. Since it is possible to use the means To formulate the high proportions of polymers mentioned, the required amount of Polymer applied to the hair with a comparatively small amount of water be so that the drying time in a remains acceptable range.
  • the re-washability of the hair treatment agent is thereby significantly increased that they also contain water-soluble polymers.
  • Water-soluble is to be understood to mean that the in the invention Hair treatment agent contained amount of this polymer at room temperature is water soluble. As a rule, these are polymers, listed in detail below significantly more than 1% by weight soluble in water.
  • the water-soluble polymers in the hair treatment compositions used according to the invention are preferred in amounts of 0.05 to 5% by weight, based on the total agent contain. In many cases, amounts of approximately 1% by weight or less are already based on the total mean, sufficient.
  • water-soluble polymers in amounts of 1 to 20 wt .-%, based on the dispersed, insoluble polymer.
  • This water-soluble polymer can also be used as a stabilizing agent in the Emulsion polymerization of the insoluble polymers are used, that is, already at Preparation of the insoluble polymer can be added. Usually it will only added when formulating the hair treatment agent.
  • Suitable amphoteric polymers are, for example, the octylacrylamide / methyl methacrylate / tert available under the names Amphomer R and Amphomer R LV-71 (DELFT NATIONAL). Butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate copolymers, the use of which, however, is generally limited to agents which are neutral or alkaline.
  • Suitable zwitterionic polymers are, for example, the polymers disclosed in German patent applications DE 39 29 973, DE 21 50 557, DE 28 17 369 and DE 37 08 451.
  • Acrylamidopropyltimethylammonium chloride / acrylic acid or methacrylic acid copolymers and their alkali and ammonium salts are particularly preferred zwitterionic polymers.
  • Other suitable zwitterionic polymers are methacroylethylbetaine / methacrylate copolymers, which are commercially available under the name Amersette R (AMERCHOL).
  • anionic is also Polymers are usually limited to neutral or alkaline solutions.
  • Cationic polymers are only suitable as soluble polymers in exceptional cases.
  • water-insoluble polymer contains ionic groups, it has proved to be useful if the water-soluble polymer is non-ionic or of is the same ionogenicity.
  • the combination of dispersed anionic polymers and dissolved anionic polymers proved to be particularly advantageous. Furthermore, it is in In many cases, it is preferable that the soluble polymer only be finished otherwise add the prepared preparation.
  • the other constituents of the hair treatment compositions used according to the invention are depending on the type of hair treatment product.
  • Preferred hair treatment agents used according to the invention are those which follow remain on the hair after use. These are in particular hair fixers, hair sprays and blow waves. Such agents can also be used as a propellant Foam aerosol formulated.
  • the coagulate-free milky polymer dispersion had a viscosity of approx. 3000 mPas; the glass transition temperature of the dispersed polymer was 20 ° C.
  • Disponil R FES 993 fatty alcohol polyglycol ether sulfate with an active substance content of approx. 30% in water (HENKEL)
  • HENKEL fatty alcohol polyglycol ether sulfate with an active substance content of approx. 30% in water
  • the organic phase of the emulsion consisted of 152 g butyl acrylate, 194 g methyl methacrylate and 10 g methacrylic acid
  • the aqueous phase consisted of 150 g deionized water, 18.5 g Disponil R FES 993 and 1 g potassium peroxydisulfate
  • the emulsion was prepared by stirring in a metering vessel and kept stable by stirring further. During the metering, the temperature of the batch was kept at values just below + 85 ° C. by external cooling. After the feed had ended, the mixture was stirred at +85 ° C. for a further 20 minutes.
  • the glass temperature of the dispersed polymers was approx. 20 ° C.
  • the weighed, dry strand was in the polymer dispersion to be examined (each 5 wt .-% polymer) immersed, with repeated immersion and Taking out an even distribution is ensured.
  • the excess Polymer dispersion was stripped between the thumb and forefinger, and the streak to a weight gain of approx. 0.3 g (based on the untreated strand) set.
  • the wet strand was wound on a spiral wrap (0 / approx. 7 mm) wound up and dried overnight. The curl was then unwound and 24 For hours at 22 ° C and 90% rel. Unhooked air humidity.
  • Curl retention values of 58 were obtained with the dispersions according to Examples 1.2 and 1.3 or 60% received.
  • a good curl retention level is also achieved when these dispersions are varied get the specified Tg range.
  • the films are too soft at very low Tg values, too brittle at very high Tg values; in both cases the curl retention values also fall significantly.
  • Dispersions according to Examples 1.1 and 1.2 were easy to wash out.
  • a dispersion according to Example 1.3 still had residues.
  • the addition of 1% Luviskol R VA 64 vinyl acetate-vinyl pyrrolidone copolymer (BASF)
  • BASF vinyl acetate-vinyl pyrrolidone copolymer

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  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Birds (AREA)
  • Epidemiology (AREA)
  • Cosmetics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

PCT No. PCT/EP95/01437 Sec. 371 Date Oct. 25, 1996 Sec. 102(e) Date Oct. 25, 1996 PCT Filed Apr. 18, 1995 PCT Pub. No. WO95/28908 PCT Pub. Date Nov. 2, 1995A process for treating hair by applying thereto a composition in the form of an aqueous dispersion of a water-insoluble polymer having a glass transition temperature of -20 DEG C. to +70 DEG C. wherein the water-insoluble polymer is formed from monomers selected from the group consisting of esters of acrylic acid, esters of methacrylic acid and styrene, and the composition further contains a water-soluble polymer.

Description

Gegenstand der Erfindung ist die Verwendung eines unlöslichen Polymers mit einer Glasübergangstemperatur zwischen -20 und + 70°C, bestehend im wesentlichen aus Monomeren, ausgewählt aus der Gruppe, die Ester der Acrylsäure, Ester der Methacrylsäure und Styrol umfaßt in Haarbehandlungsmitteln, zur Behandlung von Haaren mit der Maßgabe, daß die Haarbehandlungsmittel, enthaltend übliche kosmetische Bestandteile, in Form einer wäßrigen Dispersion dieses Polymeren vorliegen, weiterhin ein wasserlösliches Polymer enthalten und Wasser als einziges Lösungsmittel enthalten.The invention relates to the use of an insoluble polymer with a Glass transition temperature between -20 and + 70 ° C, consisting essentially of Monomers selected from the group consisting of esters of acrylic acid and esters of Methacrylic acid and styrene include in hair treatment products, for the treatment of Hair with the proviso that the hair treatment composition containing conventional cosmetic Components present in the form of an aqueous dispersion of this polymer continue contain a water-soluble polymer and contain water as the only solvent.

Haarbehandlungsmittel in Form wäßriger Lösungen oder Emulsionen von Polymeren mit Acrylatmonomeren sind beispielsweise aus den internationalen Patentanmeldungen WO 94/02112 und WO/01079 sowie der europäischen Patentanmeldung 0 590 604 bekannt. Wäßrige Haarbehandlungsmittel, die wasserunlösliche Polymere sowie für diese geeignete wasserunlösliche Lösungsmittel enthalten, sind aus der internationalen Patentanmeldung WO 92/21319 bekannt. Die internationalen Patentanmeldungen WO 91/15187 und WO 91/15186 offenbaren wäßrige Haarbehandlungsmittel, die Polymere mit bestimmten Löslichkeitsparametern sowie nichtwäßrige Lösungsmittel zur Solubilisierung dieser Polymere enthalten.Hair treatment agent in the form of aqueous solutions or emulsions of polymers with Acrylate monomers are, for example, from international patent applications WO 94/02112 and WO / 01079 as well as European patent application 0 590 604. Aqueous hair treatment products, the water-insoluble polymers and for these Suitable water-insoluble solvents are from the international Patent application WO 92/21319 known. The international patent applications WO 91/15187 and WO 91/15186 disclose aqueous hair treatment agents, the polymers with certain solubility parameters as well as non-aqueous solvents Solubilization of these polymers included.

Weiterhin bekannt aus der deutschen Offenlegungsschrift 42 24 761 ist die Verwendung wasserlöslicher oder wasserdispergierbarer Polykondensate mit Glastemperaturen oberhalb von +20 °C in Haarbehandlungsmitteln.The use is also known from German Offenlegungsschrift 42 24 761 water-soluble or water-dispersible polycondensates with glass transition temperatures above +20 ° C in hair treatment products.

Schließlich sind aus der Publikation CB-14B der Firma Eastman Chemical Company Haarsprays in Form wasserbasierter Polyesterdispersionen bekannt. Diese haben den Nachteil, daß bei hohen Polymerkonzentrationen häufig bereits nach kurzer Zeit die Düsen der Applikationsbehälter, insbesondere bei Pumpsprays, verstopfen. Daher können diese Polymeren bei Konsumentenprodukten nur in relativ geringen Konzentrationen eingesetzt werden, so daß beim Aufbringen der benötigten Polymermengen auf das Haar gleichzeitig eine große Wassermenge auf das Haar aufgebracht wird. Finally, from Eastman Chemical Company's CB-14B publication Hair sprays known in the form of water-based polyester dispersions. These have that Disadvantage that the high polymer concentrations often after a short time Block the nozzles of the application container, especially with pump sprays. Therefore can these polymers in consumer products only in relatively low concentrations be used so that when applying the required amounts of polymer to the hair a large amount of water is applied to the hair at the same time.

Die genannten Druckschriften liefern aber keinerlei Hinweise auf die besonders vorteilhaften Eigenschaften der erfindungsgemäßen Mittel.However, the mentioned publications do not provide any references to the particular advantageous properties of the agents according to the invention.

Die erfindungsgemäß verwendeten Haarbehandlungsmittel liegen in Form wäßriger Dispersionen vor und enthalten ein unlösliches Polymeres.The hair treatment agents used according to the invention are in the form of aqueous dispersions before and contain an insoluble polymer.

Unter wäßrigen Dispersionen im Sinne der Erfindung sind solche Dispersionen zu verstehen, deren äußere Phase überwiegend aus Wasser besteht, wobei Wasser das einzige Lösungsmittel ist.In the context of the invention, aqueous dispersions include such dispersions understand, whose outer phase consists predominantly of water, water being the only one Is solvent.

Ein Polymer ist dann unlöslich im Sinne der Erfindung, wenn es bei Raumtemperatur in Wasser zu weniger als 1 Gew.-% löslich ist.A polymer is insoluble in the sense of the invention if it is in at room temperature Water is less than 1 wt .-% soluble.

Die erfindungsgemäß eingesetzten wasserunlöslichen Polymeren weisen Glasübergangstemperaturen zwischen -20 °C und +70 °C auf. Polymeren mit Glasübergangstemperaturen zwischen -10 °C und +50 °C, insbesondere zwischen +10 °C und +30 °C, sind bevorzugt.The water-insoluble polymers used according to the invention have glass transition temperatures between -20 ° C and +70 ° C. Polymers with glass transition temperatures between -10 ° C and +50 ° C, especially between +10 ° C and +30 ° C are preferred.

Die erfindungsgemäß eingesetzten wasserunlöslichen Polymeren bestehen im wesentlichen, d. h. zu mindestens 80 Gew.-%, bezogen auf das Polymere, aus Estern der Acrylsäure und/oder Methacrylsäure und/oder Styrol.The water-insoluble polymers used according to the invention consist of essential, d. H. to at least 80 wt .-%, based on the polymer, from esters of Acrylic acid and / or methacrylic acid and / or styrene.

Als Ester der Acryl- bzw. Methacrylsäure kommen alle bekannten Ester dieser Säuren mit linearen und verzweigten, gesättigten und ungesättigten aliphatischen Alkoholen, aromatischen Alkoholen und aliphatisch-aromatischen Alkoholen in Betracht. Bevorzugt sind Ester mit linearen und verzweigten, gesättigten und ungesättigten aliphatischen Alkoholen mit 1 bis 22 Kohlenstoffatomen. Solche Alkohole sind beispielsweise Methanol, Ethanol, n- und iso-Propanol, n- und iso-Butanol-1, n-Pentanol-1, n-Hexanol-1, n-Heptanol-1, n-Octanol-1, n-Octanol-2, n-Decanol-1, n-Dodecanol-1 (Laurylalkohol), Myristylalkohol, Cetylalkohol, Stearylalkohol, Behenylalkohol, Oleylalkohol und Linoleylalkohol. Besonders bevorzugt sind Alkohole mit 1 bis 6, insbesondere mit 1 bis 4, Kohlenstoffatomen.All known esters of these acids come as esters of acrylic or methacrylic acid linear and branched, saturated and unsaturated aliphatic alcohols, aromatic alcohols and aliphatic-aromatic alcohols. Prefers are esters with linear and branched, saturated and unsaturated aliphatic Alcohols with 1 to 22 carbon atoms. Such alcohols are, for example Methanol, ethanol, n- and iso-propanol, n- and iso-butanol-1, n-pentanol-1, n-hexanol-1, n-heptanol-1, n-octanol-1, n-octanol-2, n-decanol-1, n-dodecanol-1 (lauryl alcohol), Myristyl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, oleyl alcohol and Linoleyl. Alcohols with 1 to 6, in particular with 1 to, are particularly preferred 4, carbon atoms.

Erfindungsgemäß ebenfalls verwendbar, wenngleich weniger bevorzugt, sind die Ester der Acryl- und Methcrylsäure mit den entsprechenden alkoxylierten, insbesondere ethoxylierten Alkoholen. Dabei können Alkoxylierungsgrade von 1 bis etwa 10 vorliegen. Also usable according to the invention, although less preferred, are the esters acrylic and methacrylic acid with the corresponding alkoxylated, in particular ethoxylated alcohols. Degrees of alkoxylation of from 1 to about 10 can be present.

Styrole im Sinne der Anmeldung sind auch Verbindungen, die eine kurzkettigte Alkylgruppe, insbesondere eine Methylgruppe, am α-C-Atom der Vinylgruppe aufweisen. Der Gehalt an Styrolgruppen im Polymer wird bevorzugt auf weniger als 70 Gew.-%, bezogen auf das Polymere, begrenzt, da es sonst unter Umständen schwierig ist, Polymere mit Glastemperaturen in dem genannten Bereich zu erhalten.Styrenes as defined in the application are also compounds that have a short chain Have alkyl group, especially a methyl group, on the α-C atom of the vinyl group. The content of styrene groups in the polymer is preferably less than 70% by weight, based on the polymer, limited, since it may otherwise be difficult, polymers with glass temperatures in the range mentioned.

Es ist ein besonderer Vorteil, daß erfindungsgemäß Polymere eingesetzt werden können, die nur aus wenigen Monomeren bestehen. So weisen Mittel mit Homopolymeren oder Copolymeren aus nur zwei Monomeren überraschend gute Eigenschaften aus. Es kann daher bevorzugt sein, im Rahmen der erfindungsgemäßen Lehre solche Homo- oder Copolymeren einzusetzen.It is a particular advantage that polymers can be used according to the invention which consist of only a few monomers. So agents with homopolymers or Copolymers of only two monomers have surprisingly good properties. It can therefore be preferred in the context of the teaching according to the invention such homo- To use copolymers.

Die wasserunlöslichen Polymere enthalten daher auch bevorzugt neben den Acrylsäureestern, Methacrylsäureestern und Styrolen keine weiteren Bausteine, wobei Verunreinigungen der Monomeren und Verbindungen, die den Kettenabbruch bewirken, nicht als weitere Bausteine angesehen werden.The water-insoluble polymers therefore also preferably contain in addition to Acrylic acid esters, methacrylic acid esters and styrenes are no further components, where Impurities in the monomers and compounds which cause the chain termination, should not be considered as additional building blocks.

Es hat sich jedoch gezeigt, daß auch Polymere, die bis zu 20 Gew.-%, insbesondere bis zu 10 Gew.-%, an weiteren Bausteinen aufweisen, erfindungsgemäß verwendet werden können. Solche weiteren Bausteine können sein:

  • Acrylamide und Methacrylamide,
  • Acrylsäure, Methacrylsäure und deren Alkalimetall-, Erdalkalimetall-, Aluminium-, Ammonium- und Alkylolammoniumsalze,
  • Crotonsäure, deren Ester und Alkalimetall-, Erdalkalimetall-, Aluminium-, Ammonium- und Alkylolammoniumsalze,
  • Vinyl- und Allylverbindungen,
  • aminogruppenhaltige Monomere.
However, it has been found that polymers which have up to 20% by weight, in particular up to 10% by weight, of other building blocks can also be used according to the invention. Such additional building blocks can be:
  • Acrylamides and methacrylamides,
  • Acrylic acid, methacrylic acid and their alkali metal, alkaline earth metal, aluminum, ammonium and alkylolammonium salts,
  • Crotonic acid, its esters and alkali metal, alkaline earth metal, aluminum, ammonium and alkylolammonium salts,
  • Vinyl and allyl compounds,
  • monomers containing amino groups.

Dabei traten die erfindungsgemäßen Vorteile in der Regel nur bei solchen Polymeren auf, bei denen der jeweilige Anteil der weiteren Bausteine auf weniger als 5 Gew.-%, bezogen auf das Polymer, begrenzt war. Ebenso hat sich gezeigt, daß es bei Einbeziehung ionischer Bausteine vorteilhaft ist, wenn entweder nur kationische oder nur anionische Bausteine im Polymer vertreten waren. Diese Polymeren wiesen deutlich bessere Eigenschaften auf als solche, in denen sowohl anionische als auch kationische Bausteine vertreten waren. The advantages according to the invention generally only occurred with such polymers in which the respective proportion of the further components is less than 5% by weight was limited to the polymer. It has also been shown that when it is included Ionic building blocks is advantageous if either only cationic or only anionic Building blocks were represented in the polymer. These polymers had significantly better ones Properties based on those in which both anionic and cationic building blocks were represented.

Bei der Auswahl der Monomeren und der fakultativen weiteren Bausteine ist unbedingt darauf zu achten, daß die Glastemperatur im Bereich zwischen -20 °C und +70 °C liegt. Hier kann der Fachmann aufgrund der bekannten Gesetzmäßigkeiten, die zwischen den Glastemperaturen der jeweiligen Homopolymeren und den entsprechenden Copolymeren, zwanglos die notwendige Vorauswahl treffen. Bei Polymeren mit weiteren, ionischen, Bausteinen ist unbedingt darauf zu achten, daß die Löslichkeit nicht zu stark zunimmt, um die damit verbundenen Nachteile zu vermeiden.When choosing the monomers and the optional further building blocks is imperative make sure that the glass temperature is between -20 ° C and +70 ° C. Here the expert can due to the known laws that exist between the Glass transition temperatures of the respective homopolymers and the corresponding copolymers, easily make the necessary pre-selection. For polymers with other, ionic, It is essential to ensure that the solubility does not increase too much in order to to avoid the associated disadvantages.

Die mittleren Molmassen der erfindungsgemäß verwendeten Polymeren liegen in der Regel zwischen 20.000 und 2.000.000; Werte zwischen 50.000 und 500.000 haben sich als besonders vorteilhaft erwiesen. Dem Fachmann sind die Möglichkeiten, bei der Polymersynthese Molmassen in einem gewünschten Bereich zu erhalten, bekannt.The average molecular weights of the polymers used according to the invention are in the Usually between 20,000 and 2,000,000; Values between 50,000 and 500,000 have been proven to be particularly advantageous. Those skilled in the art are able to: To obtain polymer synthesis molecular weights in a desired range, known.

Die erfindungsgemäß verwendeten Haarbehandlungsmittel enthalten das unlösliche Polymere, in Abhängigkeit vom Typ des Haarbehandlungsmittels, der keinen Einschränkungen unterliegt, bevorzugt in Mengen von 0,1 bis 30 Gew.-%, insbesondere 1 bis 20 Gew.-%, bezogen auf das gesamte Mittel.The hair treatment compositions used according to the invention contain the insoluble polymer, depending on the type of hair treatment product that has no restrictions is subject to, preferably in amounts of 0.1 to 30% by weight, in particular 1 to 20% by weight, based on the total mean.

Selbst bei höheren Konzentrationen, d.h. bei Konzentrationen oberhalb von etwa 10 %, zeichnen sich die erfindungsgemäßen Mittel im Vergleich zu Mitteln mit gelösten Polymeren durch sehr niedrige Viskositäten aus. Da es so möglich ist, Mittel mit den genannten hohen Anteilen an Polymeren zu formulieren, kann die erforderliche Menge an Polymer mit einer vergleichsweise geringen Menge an Wasser auf das Haar aufgebracht werden, so daß bei auf dem Haar verbleibenden Mitteln die Trocknungszeit in einem akzeptablen Bereich bleibt.Even at higher concentrations, i.e. at concentrations above about 10%, the agents according to the invention are distinguished in comparison to agents with dissolved Polymers from very low viscosities. Since it is possible to use the means To formulate the high proportions of polymers mentioned, the required amount of Polymer applied to the hair with a comparatively small amount of water be so that the drying time in a remains acceptable range.

Insbesondere die Wiederauswaschbarkeit der Haarbehandlungsmittel wird dadurch deutlich erhöht, daß diese noch zusätzlich wasserlösliche Polymere enthalten. Der Begriff "wasserlöslich" ist dabei so zu verstehen, daß die im erfindungsgemäßen Haarbehandlungsmittel enthaltene Menge dieses Polymeren bei Raumtemperatur wasserlöslich ist. In der Regel sind diese, unten im einzelnen aufgeführten, Polymeren zu deutlich mehr als 1 Gew.-% in Wasser löslich.In particular, the re-washability of the hair treatment agent is thereby significantly increased that they also contain water-soluble polymers. The term "Water-soluble" is to be understood to mean that the in the invention Hair treatment agent contained amount of this polymer at room temperature is water soluble. As a rule, these are polymers, listed in detail below significantly more than 1% by weight soluble in water.

Bevorzugt sind die wasserlöslichen Polymere in den erfindungsgemäß verwendeten Haarbehandlungsmitteln in Mengen von 0,05 bis 5 Gew.-%, bezogen auf das gesamte Mittel enthalten. In vielen Fällen sind bereits Mengen von ca. 1 % Gew.-% oder weniger, bezogen auf das gesamte Mittel, ausreichend. The water-soluble polymers in the hair treatment compositions used according to the invention are preferred in amounts of 0.05 to 5% by weight, based on the total agent contain. In many cases, amounts of approximately 1% by weight or less are already based on the total mean, sufficient.

Es ist ebenfalls bevorzugt, daß wasserlösliche Polymere in Mengen von 1 bis 20 Gew.-%, bezogen auf das dispergierte, unlösliche Polymere, einzusetzen.It is also preferred that water-soluble polymers in amounts of 1 to 20 wt .-%, based on the dispersed, insoluble polymer.

Dieses wasserlösliche Polymere kann auch als Stabilisierungsmittel bei der Emulsionspolymerisation der unlöslichen Polymeren dienen, also bereits bei der Herstellung des unlöslichen Polymeren zugegeben werden. Üblicherweise wird es aber erst bei der Formulierung des Haarbehandlungsmittels zugemischt.This water-soluble polymer can also be used as a stabilizing agent in the Emulsion polymerization of the insoluble polymers are used, that is, already at Preparation of the insoluble polymer can be added. Usually it will only added when formulating the hair treatment agent.

Erfindungsgemäß bevorzugte wasserlösliche Polymere sind nichtionogen, insbesondere, wenn sie erst bei der Formulierung des Haarbehandlungsmittels zugesetzt werden. Geeignete nichtionogene Polymere sind beispielsweise:

  • Polyvinylpyrrolidone, wie sie beispielsweise unter der Bezeichnung LuviskolR (BASF) vertrieben werden.
  • Vinylpyrrolidon/Vinylacetat-Copolymere, wie sie beispielsweise unter dem Warenzeichen LuviskolR (BASF) vertrieben werden. LuviskolR VA 64 und LuviskolR VA 73 sind bevorzugte nichtionogene Polymere.
  • Celluloseether, wie Hydroxypropylcellulose, Hydroxyethylcellulose und Methylhydroxypropylcellulose, wie sie beispielsweise unter den Warenzeichen CulminalR und BenecelR (AQUALON) vertrieben werden.
Water-soluble polymers preferred according to the invention are nonionic, in particular if they are only added when the hair treatment composition is formulated. Suitable nonionic polymers are, for example:
  • Polyvinylpyrrolidones, such as those sold under the name Luviskol R (BASF).
  • Vinyl pyrrolidone / vinyl acetate copolymers, such as those sold under the trademark Luviskol R (BASF). Luviskol R VA 64 and Luviskol R VA 73 are preferred nonionic polymers.
  • Cellulose ethers, such as hydroxypropyl cellulose, hydroxyethyl cellulose and methyl hydroxypropyl cellulose, as are sold, for example, under the trademarks Culminal R and Benecel R (AQUALON).

Geeignete amphotere Polymere sind beispielsweise die unter den Bezeichnungen AmphomerR und AmphomerR LV-71 (DELFT NATIONAL) erhältlichen Octylacrylamid/Methylmethacrylat/tert. Butylaminoethylmethacrylat/2-Hydroxypropylmethacrylat-Copolymere, deren Verwendung aber in der Regel auf neutral oder alkalisch eingestellte Mittel beschränkt ist.Suitable amphoteric polymers are, for example, the octylacrylamide / methyl methacrylate / tert available under the names Amphomer R and Amphomer R LV-71 (DELFT NATIONAL). Butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate copolymers, the use of which, however, is generally limited to agents which are neutral or alkaline.

Geeignete zwitterionische Polymere sind beispielsweise die in den deutschen Patentanmeldungen DE 39 29 973, DE 21 50 557, DE 28 17 369 und DE 37 08 451 offenbarten Polymerisate. Acrylamidopropyltimethylammoniumchlorid/Acrylsäure- bzw. -Methacrylsäure-Copolymerisate und deren Alkali- und Ammoniumsalze sind besonders bevorzugte zwitterionische Polymere. Weiterhin geeignete zwitterionische Polymere sind Methacroylethylbetain/Methacrylat-Copolymere, die unter der Bezeichnung AmersetteR (AMERCHOL) im Handel erhältlich sind. Suitable zwitterionic polymers are, for example, the polymers disclosed in German patent applications DE 39 29 973, DE 21 50 557, DE 28 17 369 and DE 37 08 451. Acrylamidopropyltimethylammonium chloride / acrylic acid or methacrylic acid copolymers and their alkali and ammonium salts are particularly preferred zwitterionic polymers. Other suitable zwitterionic polymers are methacroylethylbetaine / methacrylate copolymers, which are commercially available under the name Amersette R (AMERCHOL).

Erfindungsgemäß geeignete anionische Polymere sind u. a.:

  • Vinylacetat/Crotonsäure-Copolymere, wie sie beispielsweise unter den Bezeichnungen ResynR (NATIONAL STARCH), LuvisetR (BASF) und GafsetR (GAF) im Handel sind.
  • Vinylpyrrolidon/Vinylacrylat-Copolymere, erhältlich beispielsweise unter dem Warenzeichen LuviflexR (BASF). Ein bevorzugtes Polymer ist das unter der Bezeichnung LuviflexR VBM-35 (BASF) erhältliche Vinylpyrrolidon/Acrylat-Terpolymere.
  • Acrylsäure/Ethylacrylat/N-tert.Butylacrylamid-Terpolymere, die beispielsweise unter der Bezeichnung UltraholdR strong (BASF) vertrieben werden.
Anionic polymers suitable according to the invention include:
  • Vinyl acetate / crotonic acid copolymers, as are commercially available, for example, under the names Resyn R (NATIONAL STARCH), Luviset R (BASF) and Gafset R (GAF).
  • Vinyl pyrrolidone / vinyl acrylate copolymers, available, for example, under the trademark Luviflex R (BASF). A preferred polymer is the vinylpyrrolidone / acrylate terpolymers available under the name Luviflex R VBM-35 (BASF).
  • Acrylic acid / ethyl acrylate / N-tert-butyl acrylamide terpolymers, which are sold, for example, under the name Ultrahold R strong (BASF).

Zur Erzielung der erfindungsgemäßen Vorteile ist auch die Verwendung anionischer Polymerer in der Regel auf neutral oder insbesondere alkalisch eingestellte Lösungen begrenzt.To achieve the advantages according to the invention, the use of anionic is also Polymers are usually limited to neutral or alkaline solutions.

Kationische Polymere sind nur in Ausnahmefällen als lösliche Polymere geeignet.Cationic polymers are only suitable as soluble polymers in exceptional cases.

In den Fällen, in denen das wasserunlösliche Polymere ionische Gruppen enthält, hat es sich als zweckmäßig erwiesen, wenn das wasserlösliche Polymere nichtionogen oder von gleicher Ionogenität ist.In cases where the water-insoluble polymer contains ionic groups, it has proved to be useful if the water-soluble polymer is non-ionic or of is the same ionogenicity.

In einigen Fällen hat sich die Kombination dispergierter anionischer Polymerer und gelöster anionischer Polymerer als besonders vorteilhaft erwiesen. Weiterhin ist es in vielen Fällen vorzuziehen, das lösliche Polymer erst der ansonsten fertig zusammengestellten Zubereitung zuzugeben.In some cases, the combination of dispersed anionic polymers and dissolved anionic polymers proved to be particularly advantageous. Furthermore, it is in In many cases, it is preferable that the soluble polymer only be finished otherwise add the prepared preparation.

Die weiteren Bestandteile der erfindungsgemäß verwendeten Haarbehandlungsmittel sind von der Art des Haarbehandlungsmittels abhängig. Prinzipiell umfassen die erfindungsgemäß verwendeten Formulierungen alle bekannten Arten von Haarbehandlungsmitteln wie z. B. Haarfestiger, Haarsprays, Fönwellen, Haarshampoos, Haarspülungen, Haarkonditioniermittel, Haarkuren, Dauerwellmittel, und Haarfärbemittel.The other constituents of the hair treatment compositions used according to the invention are depending on the type of hair treatment product. In principle, these include Formulations used according to the invention all known types of hair treatment agents such as B. hair set, hair sprays, hair dryer, hair shampoos, hair rinses, Hair conditioners, hair treatments, permanent waving agents, and hair dyes.

Bevorzugte erfindungsgemäß verwendete Haarbehandlungsmittel sind solche, die nach der Anwendung auf dem Haar verbleiben. Dies sind inbesondere Haarfestiger, Haarsprays und Fönwellen. Solche Mittel können mit Hilfe eines Treibmittels auch als Schaumaerosol formuliert sein.Preferred hair treatment agents used according to the invention are those which follow remain on the hair after use. These are in particular hair fixers, hair sprays and blow waves. Such agents can also be used as a propellant Foam aerosol formulated.

Weitere Bestandteile der erfindungsgemäßen Mittel können beispielsweise sein:

  • anionische Tenside, wie beispielsweise Fettalkylsulfate und -ethersulfate,
  • kationische Tenside, wie beispielsweise quartäre Ammoniumverbindungen,
  • zwitterionische Tenside, wie beispielsweise Betaine,
  • ampholytische Tenside,
  • nichtionogene Tenside, wie beispielsweise Alkylpolyglycoside und ethoxylierte Fettalkohole,
  • Strukturanten wie Glucose und Maleinsäure,
  • haarkonditionierende Verbindungen wie Phospholipide, beispielsweise Sojalecithin, Ei-Lecithin und Kephaline, sowie Silikonöle,
  • Proteinhydrolysate, insbesondere Elastin-, Kollagen-, Keratin-, Milcheiweiß-, Sojaprotein- und Weizenproteinhydrolysate, deren Kondensationsprodukte mit Fettsäuren sowie quaternisierte Proteinhydrolysate,
  • Parfümöle, Dimethylisosorbid und Cyclodextrine,
  • Lösungsvermittler, wie Ethanol, Isopropanol, Ethylenglykol, Propylenglykol, Glycerin und Diethylenglykol,
  • Farbstoffe,
  • Antischuppenwirkstoffe wie Piroctone Olamine und Zink Omadine,
  • weitere Substanzen zur Einstellung des pH-Wertes,
  • Wirkstoffe wie Panthenol, Allantoin, Pyrrolidoncarbonsäuren und deren Salze, Pflanzenextrakte und Vitamine,
  • Lichtschutzmittel,
  • Konsistenzgeber wie Zuckerester, Polyolester oder Polyolalkylether,
  • Fette und Wachse, wie Walrat, Bienenwachs, Montanwachs, Paraffine und Fettalkohole,
  • Fettsäurealkanolamide,
  • Komplexbildner wie EDTA, NTA und Phosphonsäuren,
  • Quell- und Penetrationsstoffe wie Glycerin, Propylenglykolmonoethylether, Carbonate, Hydrogencarbonate, Guanidine, Harnstoffe sowie primäre, sekundäre und tertiäre Phosphate,
  • Trübungsmittel wie Latex,
  • Perlglanzmittel wie Ethylenglykolmono- und -distearat,
  • Treibmittel wie Propan-Butan-Gemische, N2O, Dimethylether, CO2 und Luft sowie
  • Antioxidantien,
  • direktziehende Farbstoffe,
  • sogenannte Kuppler- und Entwicklerkomponenten als Oxidationsfarbstoffvorprodukte,
  • Reduktionsmittel wie z.B. Thioglykolsäure und deren Derivate, Thiomilchsäure, Cysteamin, Thioäpfelsäure und α-Mercaptoethansulfonsäure,
  • Oxidationsmittel wie Wasserstoffperoxid, Kaliumbromat und Natriumbromat.
Further components of the agents according to the invention can be, for example:
  • anionic surfactants, such as, for example, fatty alkyl sulfates and ether sulfates,
  • cationic surfactants, such as quaternary ammonium compounds,
  • zwitterionic surfactants, such as betaines,
  • ampholytic surfactants,
  • non-ionic surfactants, such as, for example, alkyl polyglycosides and ethoxylated fatty alcohols,
  • Structurants such as glucose and maleic acid,
  • hair-conditioning compounds such as phospholipids, for example soy lecithin, egg lecithin and cephalins, and silicone oils,
  • Protein hydrolyzates, in particular elastin, collagen, keratin, milk protein, soy protein and wheat protein hydrolyzates, their condensation products with fatty acids and quaternized protein hydrolyzates,
  • Perfume oils, dimethyl isosorbide and cyclodextrins,
  • Solubilizers, such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerin and diethylene glycol,
  • dyes,
  • Anti-dandruff agents such as piroctone olamine and zinc omadine,
  • other substances for adjusting the pH value,
  • Active ingredients such as panthenol, allantoin, pyrrolidone carboxylic acids and their salts, plant extracts and vitamins,
  • Light stabilizers,
  • Consistency enhancers such as sugar esters, polyol esters or polyol alkyl ethers,
  • Fats and waxes, such as walrus, beeswax, montan wax, paraffins and fatty alcohols,
  • fatty acid,
  • Complexing agents such as EDTA, NTA and phosphonic acids,
  • Swelling and penetration substances such as glycerol, propylene glycol monoethyl ether, carbonates, hydrogen carbonates, guanidines, ureas and primary, secondary and tertiary phosphates,
  • Opacifiers like latex,
  • Pearlescent agents such as ethylene glycol mono- and distearate,
  • Blowing agents such as propane-butane mixtures, N 2 O, dimethyl ether, CO 2 and air as well
  • antioxidants
  • direct dyes,
  • so-called coupler and developer components as oxidation dye precursors,
  • Reducing agents such as thioglycolic acid and its derivatives, thiolactic acid, cysteamine, thio malic acid and α-mercaptoethanesulfonic acid,
  • Oxidizing agents such as hydrogen peroxide, potassium bromate and sodium bromate.

Die folgenden Beispiele sollen die Erfindung näher erläutern. The following examples are intended to explain the invention in more detail.

BeispieleExamples 1. Herstellungsbeispiele1. Manufacturing examples 1.1 Polymerdispersion 11.1 Polymer dispersion 1

In ein Reaktionsgefäß mit Rührer, Heizung, Kühlung, Rückflußkühler, Thermometer und rührbarem Dosiergefäß wurden 445 g entionisiertes Wasser, 134 G-CrylR 5000 (wasserlösliches Vinylaromat-Acrylsäure-Copolymeres mit einer Glasübergangstemperatur von ca. 100 °C (HENKEL)) und anschließend portionsweise 30 g einer 25%igen wäßrigen Ammoniaklösung gegeben. Sodann wurde bei Raumtemperatur bis zur Bildung einer homogenen opaken Lösung gerührt. Nach mehrmaligem Evakuieren und Befüllen des Reaktionsgefäßes mit Reinststickstoff wurden 10 g Dowfax 2A1 (4-Dodecyldiphenyletherdisulfonat-Dinatriumsatz, 45 % Aktivsubstanz in Wasser (DOW)) zugegeben und der Ansatz auf 85 °C erhitzt. Dann wurden 3,5 g Ammoniumperoxidisulfat, gelöst in 18 g entionisiertem Wasser, zugesetzt und anschließend über einen Zeitraum von 75 Minuten eine Mischung, bestehend aus 185 g Methylmethacrylat, 134 g Butylacrylat und 15 g DehydrophenR 65 (Nonylphenol + 6,5 Ethylenoxid (HENKEL)), gleichmäßig zudosiert. Dabei wurde die Temperatur des Ansatzes durch Außenkühlung auf Werten knapp unterhalb von +88 °C gehalten. Zu dem Zeitpunkt, als 80 % der Monomerenemulsion zudosiert waren, wurden noch weitere 0,5 g Ammoniumperoxidisulfat, gelöst in 15 g entionisiertem Wasser, zugesetzt. Nach Beendigung des Monomerenzulaufs wurde der Ansatz noch weitere 60 Minuten bei +85 °C gerührt. Anschließend wurde auf unter +40 °C abgekühlt, die entstandene Dispersion mit 10 g Polypropylenglykol (Molmasse ca. 1000; (DOW)) versetzt und durch einen Perlonsiebbeutel mit 80 µm Maschenweite filtriert.445 g of deionized water, 134 G-Cryl R 5000 (water-soluble vinyl aromatic-acrylic acid copolymer with a glass transition temperature of approx. 100 ° C. (HENKEL)) and then into a reaction vessel with stirrer, heating, cooling, reflux condenser, thermometer and stirrable metering vessel added in portions 30 g of a 25% aqueous ammonia solution. The mixture was then stirred at room temperature until a homogeneous opaque solution was formed. After repeated evacuation and filling of the reaction vessel with high-purity nitrogen, 10 g of Dowfax 2A1 (4-dodecyldiphenyl ether disulfonate disodium set, 45% active substance in water (DOW)) were added and the batch was heated to 85.degree. Then 3.5 g of ammonium peroxydisulfate, dissolved in 18 g of deionized water, were added and then a mixture consisting of 185 g of methyl methacrylate, 134 g of butyl acrylate and 15 g of dehydrophen R 65 (nonylphenol + 6.5 ethylene oxide ( HENKEL)), evenly dosed. The temperature of the batch was kept at values just below +88 ° C by external cooling. At the time when 80% of the monomer emulsion had been metered in, a further 0.5 g of ammonium peroxydisulfate, dissolved in 15 g of deionized water, were added. After the monomer feed had ended, the mixture was stirred for a further 60 minutes at +85 ° C. The mixture was then cooled to below +40 ° C., 10 g of polypropylene glycol (molar mass approx. 1000; (DOW)) were added to the resulting dispersion and the mixture was filtered through a Perlonon sieve bag with a mesh size of 80 μm.

Die koagulatfreie milchige Polymerdispersion hatte eine Viskosität von ca. 3000 mPas; die Glastemperatur des dispergierten Polymeren lag bei 20 °C. The coagulate-free milky polymer dispersion had a viscosity of approx. 3000 mPas; the glass transition temperature of the dispersed polymer was 20 ° C.

1.2 Polymerdispersion 21.2 polymer dispersion 2

In ein Reaktionsgefäß mit Rührer, Heizung, Kühlung, Rückflußkühler, Thermometer und rührbarem Dosiergefäß wurden 445 g entionisiertes Wasser, 134 G-CrylR- 5000 (wasserlösliches Vinylaromat-Acrylsäure-Copolymeres mit einer Glasübergangstemperatur von ca. 100 °C (HENKEL)) und anschließend portionsweise 30 g einer 25%igen wäßrigen Ammoniaklösung gegeben. Sodann wurde bei Raumtemperatur bis zur Bildung einer homogenen opaken Lösung gerührt. Nach mehrmaligem Evakuieren und Befüllen des Reaktionsgefäßes mit Reinststickstoff wurden 10 g Dowfax 2A1 (4-Dodecyldiphenyletherdisulfonat-Dinatriumsalz, 45 % Aktivsubstanz in Wasser (DOW)) zugegeben und der Ansatz auf 85 °C erhitzt. Dann wurden 3,5 g Ammoniumperoxidisulfat, gelöst in 18 g entionisiertem Wasser, zugesetzt und anschließend über einen Zeitraum von 75 Minuten eine Mischung, bestehend aus 123 g Methylmethacrylat, 89 g 2-Ethylhexcylacrylat, 62 g Styrol, 45 g Butylacrylat und 15 g DehydrophenR 65 (Nonylphenol + 6,5 Ethylenoxid (HENKEL)), gleichmäßig zudosiert. Dabei wurde die Temperatur des Ansatzes durch Außenkühlung auf Werten knapp unterhalb von +88 °C gehalten. Zu dem Zeitpunkt, als 80 % der Monomerenemulsion zudosiert waren, wurden noch weitere 0,5 g Ammoniumperoxidisulfat, gelöst in 15 g entionisiertem Wasser, zugesetzt. Nach Beendigung des Monomerenzulaufs wurde der Ansatz noch weitere 60 Minuten bei +85 °C gerührt. Anschließend wurde auf unter +40 °C abgekühlt, die entstandene Dispersion mit 10 g Polypropylenglykol (Molmasse ca. 1000; (DOW)) versetzt und durch einen Perlonsiebbeutel mit 80 µm Maschenweite filtriert.In a reaction vessel with stirrer, heating, cooling, reflux condenser, thermometer and stirrable metering vessel, 445 g of deionized water, 134 G-Cryl R - 5000 (water-soluble vinyl aromatic-acrylic acid copolymer with a glass transition temperature of approx. 100 ° C (HENKEL)) and then added in portions 30 g of a 25% aqueous ammonia solution. The mixture was then stirred at room temperature until a homogeneous opaque solution was formed. After repeated evacuation and filling of the reaction vessel with ultrapure nitrogen, 10 g of Dowfax 2A1 (4-dodecyldiphenyl ether disulfonate disodium salt, 45% active substance in water (DOW)) were added and the mixture was heated to 85 ° C. Then 3.5 g of ammonium peroxydisulfate, dissolved in 18 g of deionized water, were added, and then a mixture consisting of 123 g of methyl methacrylate, 89 g of 2-ethylhexyl acrylate, 62 g of styrene, 45 g of butyl acrylate and 15 g of dehydrophene was added over a period of 75 minutes R 65 (nonylphenol + 6.5 ethylene oxide (HENKEL)), evenly metered. The temperature of the batch was kept at values just below +88 ° C by external cooling. At the time when 80% of the monomer emulsion had been metered in, a further 0.5 g of ammonium peroxydisulfate, dissolved in 15 g of deionized water, were added. After the monomer feed had ended, the mixture was stirred for a further 60 minutes at +85 ° C. The mixture was then cooled to below +40 ° C., 10 g of polypropylene glycol (molar mass approx. 1000; (DOW)) were added to the resulting dispersion and the mixture was filtered through a Perlonon sieve bag with a mesh size of 80 μm.

Es wurde eine koagulatfreie milchige Polymerdispersion mit 46,9 % Trockenrückstand (gemessen mit einer Mettler-Trocknungswaage LP 15 auf Stufe 10 über 1 Stunde) und einer Brookfield-Viskosität von ca. 1500 mPas (gemessen mit einem Brookfield-Viskosimeter RTV bei 20 °C und 20 UpM mit Spindel 2) erhalten. Der pH-Wert der Dispersion lag bei 8, die Glastemperatur des dispergierten Polymeren bei 20 °C. It became a coagulate-free milky polymer dispersion with 46.9% dry residue (measured with a Mettler drying scale LP 15 at level 10 over 1 hour) and a Brookfield viscosity of approx. 1500 mPas (measured with a Brookfield viscometer Obtain RTV at 20 ° C and 20 rpm with spindle 2). The pH of the The dispersion was 8 and the glass transition temperature of the dispersed polymer was 20 ° C.

1.3 Polymerdispersion 31.3 Polymer dispersion 3

In einem Reaktionsgefäß mit Rührer, Heizung, Kühlung, Rückflußkühler, Thermometer und rührbarem Dosiergefäß wurden 396 g entionisiertes Wasser und 1,5 g DisponilRFES 993 (Fettalkoholpolyglykolethersulfat mit einem Aktivsubstanzgehalt von ca. 30 % in Wasser (HENKEL)) auf 82 °C erhitzt.
Dann wurden 0,5 g Kaliumperoxidisulfat, gelöst in 12 g entionisiertem Wasser, hinzugegeben. Innerhalb von zwei Stunden wurde dann gleichmäßig die nachfolgend beschriebene Emulsion zudosiert. Die organische Phase der Emulsion bestand aus 152 g Butylacrylat, 194 g Methylmethacrylat und 10 g Methacrylsäure, die wäßrige Phase bestand aus 150 g entionisiertem Wasser, 18,5 g DisponilRFES 993 und 1 g Kaliumperoxidisulfat; die Emulsion wurde durch Rühren in einem Dosiergefäß hergestellt und durch Weiterrühren stabil gehalten. Während des Zudosierens wurde die Temperatur des Ansatzes durch Außenkühlung auf Werten knapp unterhalb von +85 °C gehalten. Nach beendetem Zulauf wurde der Ansatz weitere 20 Minuten bei +85 °C gerührt. Sodann wurden noch 0,5 g Kaliumperoxidisulfat, gelöst in 12 g entionisiertem Wasser, hinzugegeben und noch weitere 45 Minuten bei +85 °C gerührt. Nach dem Abkühlen auf unter +40 °C wurde die Dispersion mit ca. 5 g 12,5 %-iger Ammoniaklösung bis zu einem pH-Wert von 6,5 neutralisiert und durch einen Perlonsiebbeutel mit 80 µm Maschenweite filtriert.
396 g of deionized water and 1.5 g of Disponil R FES 993 (fatty alcohol polyglycol ether sulfate with an active substance content of approx. 30% in water (HENKEL)) were brought to 82 ° C. in a reaction vessel with stirrer, heating, cooling, reflux condenser, thermometer and stirrable metering vessel heated.
Then 0.5 g of potassium peroxydisulfate, dissolved in 12 g of deionized water, was added. The emulsion described below was then metered in uniformly within two hours. The organic phase of the emulsion consisted of 152 g butyl acrylate, 194 g methyl methacrylate and 10 g methacrylic acid, the aqueous phase consisted of 150 g deionized water, 18.5 g Disponil R FES 993 and 1 g potassium peroxydisulfate; the emulsion was prepared by stirring in a metering vessel and kept stable by stirring further. During the metering, the temperature of the batch was kept at values just below + 85 ° C. by external cooling. After the feed had ended, the mixture was stirred at +85 ° C. for a further 20 minutes. Then 0.5 g of potassium peroxydisulfate, dissolved in 12 g of deionized water, was added and the mixture was stirred at +85 ° C. for a further 45 minutes. After cooling to below +40 ° C, the dispersion was neutralized with approx. 5 g of 12.5% ammonia solution to a pH of 6.5 and filtered through a Perlon filter bag with a mesh size of 80 µm.

Es wurde eine dünnflüssige koagulatfreie milchige Polymerdispersion mit 38,3 % Trockenrückstand (gemessen mit einem Mettler IR-Trocknungsgerät auf Stufe 10 über 1 Stunde) und einer mittleren Teilchengröße von 115 nm erhalten. Die Glastemperatur der dispergierten Polymeren betrug ca. 20 °C. A low-viscosity, coagulate-free, milky polymer dispersion with 38.3% Dry residue (measured with a Mettler IR drying device at level 10 above 1 Hour) and an average particle size of 115 nm. The glass temperature of the dispersed polymers was approx. 20 ° C.

2. Anwendungstechnische Untersuchungen2. Application studies 2.1 "Curl Retention"-Test2.1 "Curl retention" test 2.1.1. Meßverfahren2.1.1. measurement methods

Die Messung wurde an 5 Haarsträhnen (# 6925 der Firma Fischbach und Miller; je 0,5 g Masse und 28 cm Länge) bei 22 °C und 90 % rel. Luftfeuchtigkeit durchgeführt.The measurement was carried out on 5 strands of hair (# 6925 from Fischbach and Miller; each 0.5 g Dimensions and 28 cm length) at 22 ° C and 90% rel. Humidity carried out.

Die gewogene, trockene Strähne wurde in die zu untersuchende Polymerdispersion (jeweils 5 Gew.-% Polymer) getaucht, wobei durch mehrmaliges Eintauchen und Herausnehmen eine gleichmäßige Verteilung sichergestellt ist. Die überschüssige Polymerdispersion wurde zwischen Daumen und Zeigefinger abgestreift, und die Strähne auf eine Gewichtszunahme von ca. 0,3 g (bezogen auf die unbehandelte Strähne) eingestellt. Sodann wurde die feuchte Strähne auf Spiralwickel (0/ ca. 7 mm) aufgewickelt und über Nacht getrocknet. Danch wurde die Locke abgewickelt und 24 Stunden lang bei 22 °C und 90 % rel. Luftfeuchtigkeit ausgehängt.The weighed, dry strand was in the polymer dispersion to be examined (each 5 wt .-% polymer) immersed, with repeated immersion and Taking out an even distribution is ensured. The excess Polymer dispersion was stripped between the thumb and forefinger, and the streak to a weight gain of approx. 0.3 g (based on the untreated strand) set. Then the wet strand was wound on a spiral wrap (0 / approx. 7 mm) wound up and dried overnight. The curl was then unwound and 24 For hours at 22 ° C and 90% rel. Unhooked air humidity.

Der "Curl Retention"-Wert ergibt sich dann aus der Beziehung: cr = (1 - l24)/(1 - lo) * 100. The "curl retention" value then results from the relationship: c r = (1 - l 24 ) / (1 - l O ) * 100.

Dabei bedeuten:

  • l: Länge der Haarsträhne zwischen 1. und 5. Wellenmitte im gezogenen Zustand
  • l24: Abstand zwischen 1. und 5. Wellenmitte nach 24stündigem Aushängen
  • lo: Abstand zwischen 1. und 5. Wellenmitte unmittelbar nach der Entfernung des Spiralwickels.
  • Here mean:
  • l: length of the strand of hair between the 1st and 5th middle of the wave when drawn
  • l 24 : Distance between the 1st and 5th shaft center after 24 hours of hanging
  • l o : Distance between the 1st and 5th center of the shaft immediately after removal of the spiral wrap.
  • Mit den Dispersionen gemäß Beispielen 1.2 und 1.3 wurden Curl-Retention-Werte von 58 bzw. 60 % erhalten.Curl retention values of 58 were obtained with the dispersions according to Examples 1.2 and 1.3 or 60% received.

    Ein gutes Curl-Retention-Niveau wird auch bei Variation dieser Dispersionen im angegebenen Tg-Bereich erhalten. Bei sehr niedrigen Tg-Werten sind die Filme zu weich, bei sehr hohen Tg-Werten zu spröde; in beiden Fällen fallen auch die Curl-Retention-Werte deutlich ab. A good curl retention level is also achieved when these dispersions are varied get the specified Tg range. The films are too soft at very low Tg values, too brittle at very high Tg values; in both cases the curl retention values also fall significantly.

    2.2.2. Auswaschbarkeit2.2.2. washability

    Haarsträhnen (# 6923 der Firma Fischbach und Miller, ca. 2 g, ca. 15 cm lang), die mit den zu untersuchenden Zubereitungen besprüht wurden (jeweils 1 g Spray, enthaltend 20 Gew.-% Polymer) wurden nach 24 Stunden mit einer Tensidlösung (10 % TexaponRN 28 (Natriumlaurylethersulfat, 28 % Aktivsubstanz in Wasser (HENKEL)) in Wasser gewaschen, getrocknet und visuell auf Rückstände geprüft.Strands of hair (# 6923 from Fischbach and Miller, approx. 2 g, approx. 15 cm long), which were sprayed with the preparations to be examined (in each case 1 g of spray containing 20% by weight of polymer), were removed after 24 hours with a Surfactant solution (10% Texapon R N 28 (sodium lauryl ether sulfate, 28% active substance in water (HENKEL)) washed in water, dried and visually checked for residues.

    Dispersionen gemäß Beispiel 1.1 und 1.2 waren gut auswaschbar.Dispersions according to Examples 1.1 and 1.2 were easy to wash out.

    Eine Dispersion gemäß Beispiel 1.3 wies noch Rückstände auf. Durch Zugabe von 1 % LuviskolR VA 64 (Vinylacetat-Vinylpyrrolidon-Copolymer (BASF)) entstand dagegen eine Dispersion, die rückstandsfrei auswaschbar ist.A dispersion according to Example 1.3 still had residues. On the other hand, the addition of 1% Luviskol R VA 64 (vinyl acetate-vinyl pyrrolidone copolymer (BASF)) resulted in a dispersion that can be washed out without leaving any residue.

    2.2.3. Versprühbarkeit2.2.3. sprayability

    Alle Dispersionen waren auch bei hohen Polymerkonzentrationen (20 %) gut versprühbar. Die Düsen verstopften auch nach längerem Verbrauch nicht.All dispersions were easy to spray even at high polymer concentrations (20%). The nozzles did not clog even after prolonged use.

    3. Anwendungsrezepturen3. Application formulations (alle Angaben sind Gewichtsteile)(all data are parts by weight) 3.1 Pumpspray3.1 pump spray

    Panthenolpanthenol 0,50.5 Parfümölperfume oil 0,20.2 LuviskolRVA64Luviskol R VA64 1,01.0 20%ige Dispersion des Polymeren gemäß Beispiel 1.120% dispersion of the polymer according to Example 1.1 ad 100ad 100

    3.2 Pumpspray3.2 Pump spray

    Panthenolpanthenol 0,50.5 Parfümölperfume oil 0,20.2 20%ige Dispersion des Polymeren gemäß Beispiel 1.220% dispersion of the polymer according to Example 1.2 ad 100ad 100

    Claims (7)

    1. The use of an insoluble polymer with a glass transition temperature of -20 to +70°C consisting essentially of monomers selected from the group comprising esters of acrylic acid, esters of methacrylic acid and styrene, in hair treatment compositions for treating hair, with the proviso that the hair treatment compositions containing typical cosmetic ingredients are present in the form of an aqueous dispersion of the polymer, additionally contain a water-soluble polymer and contain water as sole solvent.
    2. The use claimed in claim 1, characterized in that at least 90% by weight of the polymer consists of monomers from the group consisting of esters of acrylic or methacrylic acid with C1-22 alcohols and styrene, with the proviso that the content of styrene units is no more than 70% by weight, based on the polymer as a whole.
    3. The use claimed in claims 1 and 2, characterized in that the esters of acrylic and methacrylic acid are selected from the esters with C1-6 and more particularly C1-4 alcohols.
    4. The use claimed in any of claims 1 to 3, characterized in that the polymer contains at least two different monomers selected from the esters of acrylic or methacrylic acid or styrene.
    5. The use claimed in any of claims 1 to 4, characterized in that the polymer is present in the hair treatment composition in a quantity of 0.1 to 30% by weight and more particularly 1 to 20% by weight.
    6. The use claimed in any of claims 1 to 5, characterized in that the water-soluble polymer is present in quantities of 0.05 to 5% by weight, based on the composition as a whole.
    7. The use claimed in any of claims 1 to 6, characterized in that the water-soluble polymer is nonionic.
    EP95917328A 1994-04-26 1995-04-18 Hair-treatment agents Expired - Lifetime EP0758221B1 (en)

    Applications Claiming Priority (3)

    Application Number Priority Date Filing Date Title
    DE4414424A DE4414424A1 (en) 1994-04-26 1994-04-26 Hair treatment products
    DE4414424 1994-04-26
    PCT/EP1995/001437 WO1995028908A1 (en) 1994-04-26 1995-04-18 Hair-treatment agents

    Publications (2)

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    EP0758221A1 EP0758221A1 (en) 1997-02-19
    EP0758221B1 true EP0758221B1 (en) 2002-07-03

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    EP (1) EP0758221B1 (en)
    AT (1) ATE219921T1 (en)
    DE (2) DE4414424A1 (en)
    WO (1) WO1995028908A1 (en)

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    FR2774903B1 (en) * 1998-02-13 2000-04-07 Oreal COSMETIC COMPOSITION CONTAINING AN AQUEOUS DISPERSION OF INSOLUBLE PARTICLES OF POLYMERIC MATERIAL, USE AND METHOD
    DE10243037A1 (en) * 2002-09-17 2004-03-25 Henkel Kgaa Hair treatment agent contains a nonionic, crosslinked (meth)acrylate-containing polymer of average particle diameter 50-500 nm to fix the hair
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    DE4414424A1 (en) 1995-11-02
    EP0758221A1 (en) 1997-02-19
    ATE219921T1 (en) 2002-07-15
    WO1995028908A1 (en) 1995-11-02
    DE59510260D1 (en) 2002-08-08
    US6126921A (en) 2000-10-03

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